CN104609632B - Zero-discharge treating process for coking wastewater - Google Patents

Zero-discharge treating process for coking wastewater Download PDF

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CN104609632B
CN104609632B CN201510073468.8A CN201510073468A CN104609632B CN 104609632 B CN104609632 B CN 104609632B CN 201510073468 A CN201510073468 A CN 201510073468A CN 104609632 B CN104609632 B CN 104609632B
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reverse osmosis
waste water
activated carbon
water
ultrafiltration
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CN104609632A (en
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张国兴
金鸣林
刘景霞
李俊
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SHANGHAI SANFO ENGINEERING TECHNOLOGY Co Ltd
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SHANGHAI SANFO ENGINEERING TECHNOLOGY Co Ltd
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Abstract

A kind of zero-discharge treating process for coking wastewater, the step such as including biochemical treatment, activated carbon adsorption, softening crystallization, ultrafiltration membrance filter, reverse osmosis membrane filtration, spray evaporation.Present invention process process is simple, convenient operation and management, automaticity are high, operating cost is relatively low, non-secondary pollution, can effectively administer coking chemical waste water, substantially wastewater zero discharge is realized, thoroughly eliminate Organic substance, ammonia nitrogen and the salt in waste water to grade the destruction to environment, all waste water are carried out high-quality reuse simultaneously.Both full-flow process can be processed as the waste water of newly-built coal chemical enterprise, it is also possible to dock with existing coal chemical enterprise waste water treatment process.

Description

Zero-discharge treating process for coking wastewater
Technical field
The present invention relates to waste water process, particularly to a kind of zero-discharge treating process for coking wastewater.
Background technology
Coking chemical waste water be in coal coke, gas purification and coke chemicals removal process produce containing a large amount of aromatic series And the waste water of fused ring compound and heterocyclic compound (phenol cyanogen class), have that discharge capacity is big, salt concentration concentration is high, hardness Higher, Organic substance and the feature such as ammonia nitrogen concentration is high, biodegradability is poor, Organic substance complicated, intractability are big, Belong to the highly salt containing organic waste water of difficult for biological degradation.
At present, Treatment of Coking Effluent approach mainly includes diluting biochemical process, Chemical treatment method and being directly used in wet Method quenching etc..Higher containing salinity due to coking chemical waste water itself, must consume a large amount of technique to meet biochemical condition Water is diluted, additionally heterocycle and the polycyclc aromatic compound such as the phenols in waste water, naphthalene, cyanogen, pyridine, quinoline All being difficult to biodegradation, therefore dilution biochemical process not only waste water resource, and poor processing effect, water outlet tends not to Stably reaching standard.Chemical method removes the suspended impurity in waste water and organic contamination by adding a large amount of chemical agents Thing, the effluent quality of this method is unstable, reagent cost is high, can introduce secondary pollution, adds medicament also simultaneously The difficulty of follow-up desalting processing can be increased, be phased out maybe working in coordination with other process means at present and use. It is only then pollutant transfer that coking chemical waste water is directly used in wet quenching, is not effectively addressed;The opposing party The face coking chemical waste water water yield is typically much higher than supporting wet quenching water, actual and infeasible.
Along with the most harsh to the raising of environmental protection consciousness and relevant environmental regulation and industry access condition of compatriots, The pattern directly discharged after waste water carries out extensive style process is the most unworkable at coking industry.In recent years, height is sought Effect, energy-conservation Treatment of Coking Effluent, especially Recycle Technology of Waste Water is just becoming the study hotspot in industry.Due to film Developing rapidly and wide range of industrial applications of technology, uses MBR film, ultrafilter membrane and reverse osmosis membrane etc. to combine tradition raw Change, materialization group technology is increasingly becoming Treatment of Coking Effluent and the application trend in reuse field.
Chinese patent CN103112991A discloses a kind of coking wastewater processing system and coking waste water treatment method, Big single including the process of coking chemical waste water coal tar, coking chemical waste water oxidation and biochemical treatment and coking wastewater deep treatment three Unit.Wherein coking chemical waste water coal tar processing unit includes oil removal, air supporting and acid out step, mainly in order to remove difference Granular size and coal tar of different nature;Coking chemical waste water oxidation and biochemical treatment unit include one-level electrocatalytic oxidation Change, one-level precipitation, anaerobism, anoxia, aerobic, two grades of electrocatalytic oxidations, two-stage precipitation, BAF and The steps such as membrane biological reaction, main purpose is the Organic substance in treatment of Coking Wastewater;Coking wastewater deep treatment unit Filter and osmosis filtration including one-level coarse filtration, two grades of coarse filtration, one-level security personnel's filtration, nanofiltration filtration, two grades of security personnel Etc. step.Use coal tar that this open method can effectively remove in coking chemical waste water, float, Organic substance and Ammonia nitrogen, the coking chemical waste water COD value processed of final output is relatively low, can reach discharge standard.But this is open Method has the drawback that (1) complex process, flow process are tediously long, and complex operation, management difficulty are big, actual work Journey investment makes enterprise be difficult to bear with operating cost is huge;(2) nanofiltration and reverse osmosis in concentration process except receiving The impact that machine pollutes, is the most usually limited by inorganic factors such as total salinity and hardness, and is not provided with in the method Corresponding effectively except hard pretreatment measure;(3) the dense water of nanofiltration and reverse osmosis concentrated water described in are all back to front end regulation Pond, this is infeasible, because this can cause intrasystem total salinity, hardness and undegraded Organic substance in system Circulation is also enriched with rapidly, ultimately results in nanofiltration and reverse osmosis membrane system owing to osmotic pressure is too high or fouling membrane, fouling are tight Weigh and stoppage in transit of paralysing;(4) do not account for existing coke-oven plant to have gone into operation the utilization of waste water disposal facility run.
Chinese patent CN103466890A discloses a kind of coking wastewater deep treatment and reclamation set and application thereof Method, Chinese patent CN102976511A discloses the recoverying and utilizing method of coking chemical waste water film-filter concentration liquid, in State's patent CN102874990A discloses three embrane method advanced treatment process of coking waste water and equipment thereof, three above Open method all uses various preprocessing means degradation of organic substances, prevents the organic contamination of film, utilizes embrane method to coking Waste water carries out degree of depth Treatment for Reuse, reclaims the water resource of a part of high-quality.But there is common problem in them: (1) Do not account for preventing the pretreatment measure of membranous system fouling, and coking chemical waste water height salinity, high rigidity, membrance concentration, Filter process will certainly cause fouling and the pollution of film, thus cause the problem such as flux decline, the lost of life;(2) Do not hand over reverse osmosis or the outlet of nanofiltration this strand of enriching pollutants liquid of dense water or use it for blast-furnace slag cooling, punching Slag use water, coal yard dust suppression etc..This strand of enriching pollutants liquid contains the salinity of undegradable Organic substance and high concentration (TDS:10000~20000mg/L), and fouling tendency is clearly, direct discharge can cause most evil bad ring Border is destroyed, and simple reuse can make the equipment of reuse, pipeline cause corrosion and scaling and damage.
Chinese patent CN101851046A discloses a kind of coking wastewater deep treatment and full reclamation set and answers By method, the method using biochemistry, oxidation to combine plus membrane separation technique and evaporation carries out the degree of depth to coking chemical waste water Process and reach zero-emission, being that pollutant each in coking chemical waste water is degraded by one, and by complete for water after process The new processing method of reuse.But employing the method, can consume a large amount of oxidant, reagent cost is high, evaporation energy consumption is high, Not about the high rigidity removal measure in coking chemical waste water to prevent reverse osmosis membrane and fouling of evaporator, dirt from blocking up, and not Consider the coking impact on evaporation of the remaining Organic substance.
Summary of the invention
The purpose of the present invention, in that a kind of zero-discharge treating process for coking wastewater is provided.
The object of the present invention is achieved like this: a kind of zero-discharge treating process for coking wastewater, including biochemical treatment, Also include following subsequent step:
A, activated carbon adsorption
Waste water after biochemical treatment is imported activated carbon adsorber, the remaining Organic substance in waste water is adsorbed Removing;
B, softening crystallization
Waste water after the remaining Organic substance of activated carbon adsorber removing is imported and softens crystallizer, add except hard medicine Agent, removes Ca, Mg hardness of water body;
C, ultrafiltration membrance filter
Waste water after softening crystallization is imported ultrafiltration membrance filter system, carries out solid-liquid separation, solid suspension quilt Retaining, ultrafiltration permeate enters next step;
D, reverse osmosis membrane filtration
Ultrafiltration permeate is imported reverse osmosis membrane filtration system, and reverse osmosis permeate is as pure water reuse, reverse osmosis concentrated Water enters next step;
E, spray evaporation
Reverse osmosis concentrated water being imported spray evaporation system be evaporated, condensed fluid is incorporated as pure with reverse osmosis permeate Water circulation, the solid salt that evaporation obtains as side-product reuse or is sold outward.
Also including active carbon microwave regenerating unit, this active carbon microwave regenerating unit connects activated carbon adsorber;Work as work After activated carbon adsorption in property charcoal adsorption tower is saturated, it is conducted into active carbon microwave regenerating unit, utilizes microwave energy to make The Organic substance of activated carbon adsorption discharges from activated carbon capillary, makes activated carbon activity recovery, difficult degradation simultaneously Larger molecular organics is converted into degradable small organic molecule through microwave action by pyrolytic, is back to after condensation Biochemical treatment system.
Also including aerating system, this aerating system connects ultrafiltration membrance filter system, it is achieved to ultrafiltration membrance filter system Intermittent aeration cleans.
Also including sludge condensation and dewatering system, this sludge condensation and dewatering system connect softening crystallizer and ultrafilter membrane Filtration system, collects and softens the mud that crystallizer and ultrafiltration membrance filter system produce, concentrated after use filter press Machine, band filter, screw extrusion dewaterer or centrifugal dehydrator are dehydrated, the solid slag discharge after dehydration, clearly Liquid is transmitted back to ultrafiltration membrance filter system.
Described activated carbon adsorber uses outstanding fluidized bed form, and the specific surface of described activated carbon is 300~1000m2/ gram; The heating and temperature control of described active carbon microwave regenerating unit is at 150~650 DEG C.
Described softening crystallizer is equipment reaction, clarified separation organically combined, and bottom is reaction zone, and top is Settling section;Liquid upflow velocity in reaction zone is more than 35mm/s.
Described ultrafiltration membrance filter system uses immersion ultrafiltration, and the aperture of ultrafilter membrane is 0.002~0.1 μm;Ultrafilter membrane Filtered version use external-compression type filter, filter pressure is 0.01MPaG~0.1MPaG.
Described reverse osmosis membrane filtration system uses first-stage reverse osmosis film or multi-stage reverse osmosis film cascade or multistage reverse osmosis Film cascade, the salt rejection rate of reverse osmosis membrane is 90%~99.7%;The high-pressure pump of reverse osmosis membrane filtration system uses frequency conversion Control, can be adjusted according to the pollution condition of influent quality and reverse osmosis membrane.
Described spray evaporation system uses single effect evaporation or multiple-effect evaporation;Evaporation thermal source or power use steam or machinery Compressor or the hot water of more than 85 DEG C.
Due to the fact that and have employed above technical scheme so that it is compared with prior art, have the following advantages that and special Point:
1, present invention process process is simple, convenient operation and management, automaticity are high, operating cost is relatively low, nothing Secondary pollution, can effectively administer coking chemical waste water, substantially realize Zero-discharge coked wastewater, thoroughly eliminates in waste water Organic substance, ammonia nitrogen and salt grade the destruction to environment, all waste water are carried out high-quality reuse simultaneously.
2, the invention provides the regeneration of perfect pretreatment system, especially activated carbon adsorption and microwave activated carbon can Removing the Organic substance in water body, the degraded the most treatable larger molecular organics of biochemistry further, softening crystallizer can go Except the hardness in water body eliminates the fouling factor, solution Organic substance, SS, the hardness etc. of working along both lines is to ultrafilter membrane, anti- Permeable membrane and the operating fouling of spray evaporation, coking impact, drastically increase bi-membrane method in Treatment of Coking Effluent With the probability that recovery field realizes industrialization promotion.
3, evaporation uses vacuum spraying evaporation, and making evaporation of water is solid space evaporation by traditional surface evaporation, Its evaporation intensity is traditional 10~50 times, and evaporation equipment specification can be made to reduce, and can use low-grade 85 DEG C with On hot water as adding thermal medium, both reduced energy consumption, it is achieved energy-saving and cost-reducing, and can effectively eliminate in evaporation process again Bubble-related issues, it is ensured that system even running.
The present invention both can process full-flow process as the waste water of newly-built coal chemical enterprise, it is also possible to looks forward to existing coking Industry waste water treatment process docks.
Accompanying drawing explanation
Fig. 1 is the flow chart of zero-discharge treating process for coking wastewater of the present invention.
Detailed description of the invention
Embodiment 1
Coking chemical waste water after ammonia still process and the oil removal treatment of learning from else's experience is as pending raw water, water yield 100m3/ h, coking Waste water quality is as shown in table 1:
Table 1
Project Unit Numerical value
pH 9~11
Colourity Times 105
SS mg/L 65
NH4 + mg/L 274
COD mg/L 3880
BOD mg/L 1050
Ca2+ mg/L 70
TDS mg/L 3670
Oils mg/L 0.5
TOC mg/L 1233
Coking chemical waste water first returned sludge with sedimentation tank enters anaerobic reactor in the lump, and its major function is release Phosphorus, carries out ammonification to partial organic substances simultaneously;The water outlet of anaerobic reactor enters anoxic reacter and carries out denitrogenation processing, Nitrate nitrogen therein is sent here by aerobic reactor by interior circulation;Waste water after denitrogenation is introduced aerobic reaction Device, carries out the removal of COD/BOD, nitrification and absorption phosphorus at this, and a part of mixed-liquor return is to anoxic reacter; Water outlet after aerobic reaction is introduced into sedimentation tank, carries out mud-water separation, and a part for mud is back to anaerobic reactor, Supernatant enters subsequent processing units as producing water.After above-mentioned biochemical treatment system processes, the COD in waste water Being greatly lowered with ammonia nitrogen concentration, clearance respectively reaches 90% and 95%, i.e. COD in waste water < 100mg/L, Ammonia nitrogen < 25mg/L.
Bio-chemical effluent enters activated carbon adsorber, adsorbs de-further to hardly degraded organic substance remaining in waste water Removing, make the COD < 50mg/L in waste water, < 15mg/L meets subsequent ultrafiltration film, reverse osmosis membrane system enters to ammonia nitrogen Water is to Organic substance and the requirement of ammonia nitrogen.
After activated carbon adsorption certain time, adsorption capacity is the most saturated, and adsorption efficiency reduces or loses, now will absorption Saturated activated carbon imports active carbon microwave regenerating unit online.Owing to the saturated activity charcoal containing certain moisture is to inhale Wave material, the moisture vaporized expanding that when utilizing microwave heating, it is internal will adsorb Organic substance in micropore to be peeled off, blows out, The larger molecular organics of hardly-biodegradable can be converted into degradable little by the localized hyperthermia that microwave heating produces simultaneously Molecular organic, consequent a small amount of vaporization and condensation regeneration liquid waste is back to anaerobic reactor circulation biochemical treatment.
Remove organic waste water further through activated carbon adsorber and be introduced into softening crystallizer, add except hard medicine Agent, utilizes the crystallizer that softens with special construction to remove Ca, Mg hardness in water body, and crystallizer produces in water Ca2+< 20mg/L, Mg2+< 50mg/L, thoroughly eliminates Ca, Mg fouling tendency, even if making follow-up reverse osmosis membrane Concentrating 4~5 times does not has fouling dirt to block up risk yet.Crystallizer produces water and certainly flows into submerged ultrafiltration filtration system, passes through Suction pump will transmit through liquid and is collected in ultrafiltration product water tank, and the solid suspension in waste water is trapped, i.e. at membrance separation In pond, enrichment concentrates.Ultrafilter membrane uses dead-end filtration form, Water Sproading rate almost 100%.Periodically bottom membrane cisterna Carrying out spoil disposal, maintaining the solid suspension concentration in membrane cisterna is about 3%.
Needing the pH regulator that ultrafiltration is produced water to 6 before entering reverse osmosis membrane filtration system, ultrafiltration membrane permeate liquid is led to Crossing pump and squeeze into reverse osmosis membrane filtration system, reverse osmosis membrane permeate, as industrial pure water reuse, produces water water quality such as table 2 Shown in.The producing water ratio of reverse osmosis membrane is 80%, i.e. aquifer yield is 80m3/ h, filter pressure is 2.0~3.5MPa. Reverse osmosis concentrated water enters vaporizer and processes.
Table 2
Project Unit Numerical value
pH 6~9
SS mg/L < 1
NH4 + mg/L 10
COD mg/L 10
TDS mg/L < 100
Enter the reverse osmosis membrane dense water about 20m of spray evaporation system3/ h, spray evaporation uses two effect MVR evaporations. MVR evaporation is that pressure and temperature is raised, and heat content is therewith through the compression of mechanical compressor by indirect steam Increasing, the heating chamber being sent to vaporizer uses as adding vapours, makes feed liquid maintain evaporating state, and heats steaming Vapour itself transfers heat to material itself and is condensed into water.So, indirect steam to be discarded just is filled The utilization divided, has reclaimed latent heat, has improve again the thermal efficiency.MVR is used to evaporate 1m3Water only consumes about 40 degree Electricity, operating cost is only and uses the 1/3 of raw steam raising.Meanwhile, use spray evaporation, there is bigger evaporation Specific surface, evaporation efficiency is greatly improved, and evaporation is caused by the foam that Organic substance remaining in water is formed at evaporation liquid level Suppression be also eliminated.The about 20m that evaporation obtains3/ h evaporation condensate and the conduct in the lump of reverse osmosis membrane permeate Recycle-water, the solid salt that evaporation obtains as side-product reuse or is sold outward.

Claims (4)

1. a zero-discharge treating process for coking wastewater, including biochemical treatment, it is characterised in that also include following Subsequent step:
A, activated carbon adsorption
Waste water after biochemical treatment is imported activated carbon adsorber, the remaining Organic substance in waste water is adsorbed Removing;
B, softening crystallization
Waste water after the remaining Organic substance of activated carbon adsorber removing is imported and softens crystallizer, add except hard medicine Agent, removes Ca, Mg hardness of water body;
C, ultrafiltration membrance filter
Waste water after softening crystallization is imported ultrafiltration membrance filter system, carries out solid-liquid separation, solid suspension quilt Retaining, ultrafiltration permeate enters next step;
D, reverse osmosis membrane filtration
Ultrafiltration permeate is imported reverse osmosis membrane filtration system, and reverse osmosis permeate is as pure water reuse, reverse osmosis concentrated Water enters next step;
E, spray evaporation
Reverse osmosis concentrated water being imported spray evaporation system be evaporated, condensed fluid is incorporated as pure with reverse osmosis permeate Water circulation, the solid salt that evaporation obtains as side-product reuse or is sold outward;
Also including active carbon microwave regenerating unit, this active carbon microwave regenerating unit connects activated carbon adsorber;Work as work After activated carbon adsorption in property charcoal adsorption tower is saturated, it is conducted into active carbon microwave regenerating unit, utilizes microwave energy to make The Organic substance of activated carbon adsorption discharges from activated carbon capillary, makes activated carbon activity recovery, difficult degradation simultaneously Larger molecular organics is converted into degradable small organic molecule through microwave action by pyrolytic, is back to after condensation Biochemical treatment system;
Described softening crystallizer is equipment reaction, clarified separation organically combined, and bottom is reaction zone, and top is Settling section;Liquid upflow velocity in reaction zone is more than 35mm/s;
Described spray evaporation system uses single effect evaporation or multiple-effect evaporation;
Also including aerating system, this aerating system connects ultrafiltration membrance filter system, it is achieved to ultrafiltration membrance filter system Intermittent aeration cleans;
Also including sludge condensation and dewatering system, this sludge condensation and dewatering system connect softening crystallizer and ultrafilter membrane Filtration system, collects and softens the mud that crystallizer and ultrafiltration membrance filter system produce, concentrated after use filter press Machine, band filter, screw extrusion dewaterer or centrifugal dehydrator are dehydrated, the solid slag discharge after dehydration, clearly Liquid is transmitted back to ultrafiltration membrance filter system.
Zero-discharge treating process for coking wastewater the most according to claim 1, it is characterised in that: described activity Charcoal adsorption tower uses outstanding fluidized bed form, and the specific surface of described activated carbon is 300~1000m2/ gram;Described activated carbon is micro- The heating and temperature control of ripple regenerating unit is at 150~650 DEG C.
Zero-discharge treating process for coking wastewater the most according to claim 1, it is characterised in that: described ultrafiltration Membrane filtration system uses immersion ultrafiltration, and the aperture of ultrafilter membrane is 0.002~0.1 μm;The filtered version of ultrafilter membrane is adopted Filtering with external-compression type, filter pressure is 0.01MPaG~0.1MPaG.
Zero-discharge treating process for coking wastewater the most according to claim 1, it is characterised in that: described reverse osmosis Permeable membrane filtration system uses first-stage reverse osmosis film or multi-stage reverse osmosis film cascade or the series connection of multistage reverse osmosis membrane, reverse osmosis The salt rejection rate of film is 90%~99.7%;The high-pressure pump of reverse osmosis membrane filtration system uses VFC, according to water inlet The pollution condition of water quality and reverse osmosis membrane is adjusted.
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CN106336066B (en) * 2015-07-08 2020-04-24 天津三环乐喜新材料有限公司 Zero discharge system and method for neodymium iron boron permanent magnet material wastewater
CN108623085B (en) * 2017-03-18 2022-05-31 深圳市深水生态环境技术有限公司 Advanced treatment method for high-nitrogen organic wastewater membrane filtration concentrate
CN110194500A (en) * 2018-02-24 2019-09-03 宝武炭材料科技有限公司 A kind of system and method using the continuous absorption regeneration processing coking wastewater of active carbon
CN108928984B (en) * 2018-08-08 2021-07-20 鞍钢股份有限公司 Method for realizing zero emission of reverse osmosis strong brine in iron and steel enterprises
CN109665667A (en) * 2019-01-07 2019-04-23 郑州大学综合设计研究院有限公司 A kind of nylon66 fiber cord fabric wastewater deep treatment process
CN111606496B (en) * 2020-04-28 2022-11-25 郝东珍 Coking wastewater treatment device and method
CN111517503A (en) * 2020-05-15 2020-08-11 江苏阿尔法环保科技有限公司 COD digestion device and technology in organic wastewater
CN113772884B (en) * 2021-09-03 2022-12-13 西安交通大学 Coking wastewater treatment system and method

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CN101643294A (en) * 2008-08-04 2010-02-10 何庆 Method for treating coking wastewater
CN101659486B (en) * 2009-04-24 2012-11-28 戈亮 New technique for deeply treating industrial waste water by RO membrane
CN102134129B (en) * 2010-01-25 2014-09-10 白连福 Softening process for industrial raw water
US20140094975A1 (en) * 2012-09-28 2014-04-03 Elo Nielsen Control system for a mobile water filtration unit, and related devices, components, systems and methods
CN103449668A (en) * 2013-08-30 2013-12-18 中国地质大学(武汉) Method for treating restaurant wastewater through combination of microbial decomposition and active carbon adsorption
CN203976566U (en) * 2014-06-23 2014-12-03 山东国信环境系统股份有限公司 Brine waste is processed reclamation set

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